Production of color photographic pictures



Patented Jan. 9, 1940 PATENT. OFFICE PRODUCTION OF COLOR PICT rnorocnsrmc mes Wilhelm Schneider, Dessan, Germ ny, assignor,

by mesne assignments, to

tion, Binghamton, N. Y.,

aware Agi'a Ansco Corporaa corporation of -Del- No Drawing. Application February 2, 1939, Se-

rial No. 254,235. 1938 11 Claims.

My present invention relates to the production of color photographic pictures.

It has been proposed to produce color photographic pictures by color development with use of dyestuff components having reactive methylcue-groups which in the development of a latent silver image by means of a developer containing a free amino-group, for example para-phenylenediamine, para-aminophenol or derivatives 1 thereof, yield a dyestufi image in the place of the silver image. :Such components are, for example, acetoacetic ester and its derivatives, pyrazolones, isoxazolones, para-nitrobenzylcyanide r or malonitrile; of these pyrazolones and isoxazolones are principally used for producing red dyestufi pictures. The compounds of these lastnamed classes, however, do not fulfill all requirements in respect of variation of color tint in the production of multi-color pictures by the reversal process or copying process.

It is one object of my invention to provide a photographicmaterial capable of yielding very beautiful purple-red tints by development in co or.

A further object of this invention is to provide a photographic material one emulsion layer of which contains a-indolinone as the dyestufi component. Another object is the provision of a photographic material which comprises .an emulsion layer containing a-indolinone substituted at the nitrogen atom.

Yet another object is to provide a photographic material comprising an emulsion layer which contains a-indolinone substituted in the benzene nucleus.

A still further object is to provide a photo- Q graphic material having an emulsion layer which contains a-indolinone substituted by 'alkyl droxy groups or nitro groups.

Yet another object is the provision of a photogroups, alkoxy groups, aryl groups,'halogen, hy-

In Germany February 5,

diffusion in the binding agent of the emulsion by introducing particular groups.

Other objects of 'my invention will appear from the description following hereinafter.

The groups which impart fastness to diffusion may be introduced, for example, by the methods described in the U. S. Patents 2,179,238, 2,178,612 and 2,179,244 and 'U. S. Patent applications 94,340 filed August 5, 1936, 159,518 filed August 17, 1937, 164,499 filed September 18, 1937, 166,832 filed October 1, 1937, 171,705 filed October 29, 1937, 175,285 filed November 18, 1937, 176,058 filed November 23, 1937 and 191,952 filed February 23, 1938.

The last named application describes components which contain in addition to a group rendering the component fast to diffusion a solubilizing group such as a carboxy group. The components are prepared by reacting the internal anhydride of apolybasic organic acid, such as the anhydrides of maleic acid, succinic acid, pyro-tartaric acid and the like containing for example a long aliphatic chain 1. e. of at least 5 carbon atoms such as octadecylene, isodecylene, iso-nonylene and the like with a color former containing a reactive group such as an aminoor hydroxy group. The ring of the anhydride is thereby split in such a manner that one C0- group'units with the reactive group and the other forms a 'carboxy group. As the color former there may be used p-amino-aceto-acetic' anilide, 4 q amino 1-phenyl-3-methyl-5-pyrazolone,- 1- amiho-S-naphthol .and the like. As the. anhydride there may be used octadecylene succinic acid anhydride, u-dodecyl-m-hexahydrobenzenepyro-tartaric acid anhydride and the like.

Also the nitrogen atom of a-indolinone may carry a radicle prescribed in one or other of the foregoing applications, for instance an undecyl group. Furthermore, as described in the speciflcation of the U. S. Patent application Ser. No.

171,701 filed October 29, 1937, the molecule of the dyestufi component maybe in the form of a chain. Asexplained in the mentioned specifications, radicles lending fastness to diffusion may be introduced in known manner, for example, by

way of amino-, hydroxyor carbonyl-groups with formation of acid amides or esters. It is also 1 be cast in the form of single layers or in the form of multiple layers on one or both sides of a support to produce the multi-layer material, the

the spectrum.

Alternatively, the photographic emulsions having different dyestuif components may be distributed in particles on a support. With the aid of this material screen pictures may be made.

The silver halide emulsion layers provided with layers being sensitized for differentregions of the dyestuif components may be combined with NH N Ali-111a:

The dyestufl component is produced in following manner: d-indolinone is dissolved in concentrated 4 sulfuric acid and nitrated by addition of 1 mol of sodium nitrate with cooling. The reaction product is precipitated by pouring out the mixture on ice and after recrystallizing from water is reduced with stannous chloride and hydrochloric acid. The tin is removed with hydrogen sulfide and the whole is concentrated by evaporation. The reaction product is then acylated with 1 moi of oleic acid chloride in pyr i e. After 7 sulfonation with sulfuric acid containing 30 per cent S0; with cooling a product easily soluble in water is obtained. This dyestufl component is then dissolved in a solution of sodium carbonate and added to a silver halide emulsion.

so a Example 2 A of the 'followmg formula may be Q incorporated in a photographic layer: I i

m I on,-

I to N Stearylaniline is acylated with chloracetyl chloride. The reaction product thus obtained is mixed with aluminium chloride and heated to 7 200 until the hydrochloric acid is completely re- -moved. To the mixture there is added'ice and the dyestuff component is obtained by extraction with ether. The component is then dissolved inmethanol andthesolutionisaddedtoasilver hhoudoenumon.

: Esample 1 mol of fi-amino-a-indolinone produced in the manner as described in-Example l iscaused to react with 1 mol of octodecylene-succinic acid 5 anhydride. The product thus obtained of the following formula L 0 10 NH N o-oni-e-coon isHu a 15 is dissolved in a solution containing sodium carbonate and this solution is added to a photographic emulsion.

Example 4 1 mol of fi-alninO-a-lndOllIlOIle produced in the manner described in Example 1 is reacted with 1 mol of abietic acid chloride. The product thus obtained of the following formula 0 NH N lo emetic acldradicle is dissolved in methanol and added to a photographic emulsion.

' I claim:

1. A photographic. silver halide emulsion con- .35

prising at least one silver halide emulsion containing a binding agent and a compound selected from the class consisting oi a-indolinone and substituted a-indolinone, said compound containing in its molecule a group capable of making said compound fast to diffusion 'in said binding agent. u

4. A photographic multi-layer material comprising at least one silver halide gelatin emulsion layer containing a compound selected from the class of a-indolinone and substituted aindolinone,-said compound containing inits U molecule a group capable of making said compound fast to diffusion in gelatin.

'5. A photographic multi-layer material comprising at least one silver halide emulsion layer containing a compound of the formula ll prising at least one silver halide emulsion layer containing a compound of the formula C1a a1 '7. A photographic multi-layer material comprising at least one silver halide emulsion layer containing a compound of the formula 8. The photographic silver halide emulsion defined in claim 2 wherein the group capable of making said compounds fast to diffusion is an aliphatic radicle of high molecular weight.

9. The photographic silver halide emulsion deflnedin claim 2 wherein the group capable of making said compounds fast to diffusion is an aliphatic radicle of high molecular weight which is linked to the indolinone nucleus by a linkage selected from the class consisting of a direct carbon to direct nuclear carbon linkage, an ester linkage and an acid amide linkage.

10. The photographic silver halide emulsion defined in claim 2 wherein the group capable of making said compounds fast to diffusion is an I aliphatic radicle containing from 18 to 22 carbon atoms. v

11. The photographic silver halide emulsion defined in claim 2 wherein the group capable of making said compounds fast to difiusion is an aliphatic radicle containing from 18 to, 22 carbon atoms and having a solubilizing group selected from the class consisting of 'sulfonic acid and carboxylic acid groups. I

WILHELM SCHNEIDER. 

